Thermoluminescent properties of Eu and RE co-doped phosphors CaGa2S4:Eu, RE (RE=Ln, excluding Pm, Eu and Lu)

The thermo-luminescence (TL) of rare earth ions RE³⁺ (RE=Ln, excluding Pm, Eu and Lu) co-doped phosphors CaGa₂S₄:Eu²⁺, RE³⁺ was studied between room temperature and 300 °C, and 3D thermo-luminescence of the phosphors were measured from room temperature to 400 °C. The basic material CaGa₂S₄:Eu²⁺, showed at least two bands in the TL glow curve. Changing the auxiliary activator RE³⁺ (rare earth ion), intensities and the positions of the TL glow curve peaks were affected significantly. For the phosphors with long afterglow, auxiliary activator such as Ce³⁺, Pr³⁺, Gd³⁺, Tb³⁺, Ho³⁺, or Y³⁺ created some new defects in these compounds at lower trap levels and enhanced their TL intensities. The Nd³⁺ or Er³⁺ auxiliary activator only enhanced TL intensities to a low extent, so these two phosphors have short persistent luminescence at room temperature. TL intensities of La³⁺, Sm³⁺, Tm³⁺ or Yb³⁺ co-doped phosphors were suppressed greatly and no afterglow was shown. The relationship between auxiliary activators and corresponding thermo-luminescence curves of phosphors CaGa₂S₄:Eu²⁺, RE³⁺ are discussed in detail. According to our results, suitable activation energy and enough high corresponding trap density are necessary for the phosphor with long afterglow.     

Emission spectra of MgSO4:Dy,MgSO4:Tm and MgSO4:Dy,Mn phosphors

MgSO₄:Dy, MgSO₄:Tm and MgSO₄:Dy,Mn thermoluminescence (TL) phosphors have been prepared and their emission spectra were measured using a linear heater and optical multichannel analyzer. Emission bands at about 480, 580 and 660 nm of MgSO₄ doped with Dy were observed in three dimension (3D) glow curve. Emission bands about 360, 460, and 660 nm were observed in a 3D glow curve of MgSO₄ doped with Tm. The emission spectra of MgSO₄:Dy and MgSO₄:Tm are attributed to the characteristic emission wavelengths from transitions of Dy³⁺ and Tm³⁺ respectively. The results show that the structures of traps in matrix materials determine the activation energy distribution and dopant energy levels of rare earth ions are related with the emission spectrum wavelengths of sulfate phosphors. The intensities of the glow peaks in both bands at about 480 and 580 nm in MgSO₄ doped Dy and Mn were dramatically reduced in comparison with that of MgSO₄ doped Dy except above 300°C. It means that the trapping structures of MgSO₄ :Dy phosphor has greatly been altered by the co-dopant Mn but no change is observed in wavelengths of the emission spectra.     

Determination of kinetic parameters of thermally stimulated luminescence of Cu-doped BaSO4

Studies of thermally stimulated luminescence (TSL) of doped BaSO₄ with Cu activator have been carried out. The polycrystalline sample of Cu-doped BaSO₄ is prepared by recrystallisation method. The characterization and elemental analysis of BaSO₄:Cu compound are carried out by X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDX). The compound has orthorhombic structure at room temperature. The TSL studies of Cu-doped BaSO₄ sample show two glow peaks at 160 and 227 °C. Comparison of TL intensity of the most intensive glow peak of Cu- and Mn-doped BaSO₄ compounds with that of undoped BaSO₄ shows that addition of Cu and Mn impurity in BaSO₄ compound enhances the TL intensity by about 9 and 3 times, respectively. Among the studied samples, namely undoped, Cu- and Mn-doped BaSO₄, Cu-doped BaSO₄ is found to be the most sensitive. The trap parameters namely order of kinetics (b), activation energy (E), frequency factor (s) and Balarin parameter (γ) associated with the most intensive glow peak, i.e. the 227 °C glow peak of BaSO₄:Cu phosphor were determined by using isothermal decay method and glow curve shape (Chen's) method and these parameters are in good agreement.     

Thermoluminescence of rare earth activated CdSO4, SrSO4 and BaSO4

The thermoluminescence (TL) of rare earth (RE) activated sulfates of Cd, Sr and Ba was studied above room temperature. Many of the phosphors prepared exhibit an extremely bright TL following X-irradiation (most notably with Sm, Eu, Tb, Dy and Tm dopants), having an efficiency comparable to that of the highest sensitivity phosphors available for TL dosimetry, and exhibiting activator-induced glow peaks between 405 and 480°K. In a given lattice, the RE³⁺ ions produce a characteristic glow peak at the same temperature (independent of the particular RE ion), whereas Eu²⁺ produces a single glow peak at a different temperature. A decrease in glow peak temperature with increasing interatomic spacing was observed in the homologous SrSO₄-BaSO₄ system - this shift being most pronounced in the Eu²⁺ -doped materials. TL emission spectra were obtained for trivalent Sm, Tb, Dy and Tm and for divalent Eu in these sulfates (and also in CaSO₄).     

Thermally stimulated luminescence studies of undoped,Cu- and Mn-doped CaSO4 compounds

Thermally stimulated luminescence (TSL) of undoped and doped CaSO₄ with activators such as Cu and Mn has been investigated. The polycrystalline samples of undoped and doped CaSO₄ are prepared by the melting method. The formation of CaSO₄ compound is confirmed by X-ray diffraction and Fourier transform infrared studies. Scanning electron microscopic studies of CaSO₄ are also carried out.

The TSL glow curves of undoped CaSO₄, Cu- and Mn-doped CaSO₄ are studied. Comparison of the thermoluminescence (TL) intensity of the most intensive glow peak of Cu-doped CaSO₄ compound with that of undoped CaSO₄ shows that addition of Cu impurity in CaSO₄ compound enhances the TL intensity by about four times. However, the addition of Mn impurity to undoped CaSO₄ increases the TL intensity by about three times when compared with that of undoped CaSO₄. The TL-dose dependence of all three samples was studied and was observed to be almost linear in the studied range of irradiation time. Among the samples studied, namely undoped CaSO₄ and Cu- and Mn-doped CaSO₄, Cu-doped CaSO₄ is found to be the most sensitive. The trap parameters, namely order of kinetics (b), activation energy (E) and frequency factor (s) associated with the most intensive glow peaks of CaSO₄:Mn, CaSO₄:Cu and CaSO₄ phosphors were determined using the glow curve shape (Chen's) method.     

Synthesis and thermoluminescence characterization of MgB4O7:Gd,Li

Magnesium tetraborate (MTB) doped with rare earth elements were synthesized by solid state sintering technique. Among the different rare earth dopants studied in this phosphor, gadolinium doped phosphors resulted in a single intense dosimetric peak at 250 °C and this is the first report in rare earth-doped MgB₄O₇ with a glow peak above 200 °C Photoluminescence (PL) and thermoluminescence (TL) studies were performed with this phosphor after exposing the powder samples to ionizing radiation. Monovalent dopants, including Na, Li and Ag, were found to increase the TL sensitivity of the MgB₄O₇:Gd phosphor without a shift in the TL peak temperature. The TL emission spectra showed characteristic emission of the host lattice, which showed an increase on doping with rare earth or monovalent codopants. The TL sensitivity, dose response curve, and post-irradiation storage stability were studied for the possible use of this material in radiation dosimetry applications. The TL parameters, such as the activation energy, the frequency factor, and the order of kinetics were determined for the Gd-doped MgB₄O₇ phosphor. The phosphor was found to be reusable after a few cycles of irradiation and annealing. The post-irradiation storage stability studies showed that this near tissue-equivalent phosphor, which has a gamma sensitivity five times that of TLD-100, is suitable for medical dosimetry applications.     

Structural analysis, TSL studies and evaluation of trapping parameters of Cu activated CaSO4

The XRD and SEM and TSL studies of the as prepared pure, Cu and Mn doped CaSO₄ have been carried out. From the comparative TSL studies it has been seen that the 137 °C glow peak of CaSO₄:Cu is superior to undoped and Mn doped CaSO₄ compounds as well as other Cu doped alkaline earth sulphates. Evaluation of trapping parameters of the most intensive glow peak Cu (0.5 mol%) doped CaSO₄ is accomplished by a technique named isothermal luminescence decay method and comparison of these parameters with the previously calculated trapping parameters by glow curve shape method (Chen’s method) have been done. It is observed that the most intensive glow peak of Cu doped CaSO₄ is found to obey second order kinetics, because of availability of vacant traps for retrapping to take place. Moreover the effect of various doping concentration of Cu on the TSL glow curve and reproducibility of Cu doped CaSO₄ has also studied.     

Energy transfer process in CaSO4:Tb,Ce phosphor

Thermoluminescence (TL) and photoluminescence studies have been carried out on CaSO₄:Tb, CaSO₄:Ce and CaSO₄:Tb,Ce phosphors with the aim of studying energy transfer process in the CaSO₄:Tb,Ce phosphor. CaSO₄:Tb,Ce shows TL peaks at 150, 220, 320 and 400°C. Changes in Tb and Ce concentrations influence the relative heights of these glow peaks. Co-doping with 0.1 mol% of Ce in CaSO₄:Tb enhances the sensitivity of 320^oC TL peak by a factor of 15. Fluorescence results show that there is energy transfer from Ce to Tb ion. The defect centres formed in CaSO₄:Tb,Ce phosphor are studied using electron spin resonance technique. The 320^oC glow peak correlates with a centre (SO₃⁻radical) with g-values: g_||=2.0061 and g_⊥=2.0026.     

Energy transfer in CaSiO3 phosphors doped with Ce3+ and Tb3+

Calcium metasilicate phosphors activated by Ce³⁺ and Tb³⁺ have been studied for their emission characteristics. In two series of phosphors, one activator was kept at its optimum value while the other was varied. In another two series, one activator was kept below its optimum value and the other was varied. Concentration quenching effects start when each activator gives its maximum emission. There is clear evidence of an energy transfer from Ce³⁺ to Tb³⁺ because the⁵ D ₃ lines appear on addition of Ce³⁺ while they were conspicuously absent when Tb³⁺ alone was present. Their absence in singly activated phosphors could not have been due to cross-relaxation. Obviously X-ray excitation does not lead to⁵ D ₃ transitions which are achieved only by energy transfer. Further, considering the features of the emission spectra and the concentrations of activators used, the transfer could only be of the dipole-dipole type.     

CaSnO3∶Tb3+绿色长余辉荧光粉的制备与发光性质的研究

采用高温固相法合成了CaSnO3∶Tb3+绿色长余辉荧光粉。利用X射线衍射分析了CaSnO3∶Tb3+物相结构。研究了Tb3+浓度对样品发光强度的影响,结果显示:随Tb3+浓度的增大,发射光谱强度先增大后减小,出现了浓度猝灭效应,Tb3+的最佳摩尔分数为0.3%。发射光谱由4个主要发射峰组成,峰中心分别位于492,546,588,623 nm处,以Tb3+的5D4→7F5(546 nm)跃迁发射为最强。对样品的温度特性进行了测量,通过对数据进行拟合得到样品的激活能为0.58 eV,陷阱深度为0.622 eV。最后,给出了CaSnO3∶Tb3+绿色长余辉荧光粉可能的余辉发光机理。     

Luminescence and evaluation of trapping parameters in NaMgSO4Cl: X (X=Cu or Ce) phosphor

Thermoluminescence (TL) characteristics of recently developed high sensitive mixed halosulphate phosphors, NaMgSO₄Cl: Cu and NaMgSO₄Cl: Ce were studied in comparison with CaSO₄: Dy in order to assess the possibility of their use in personal monitoring and TLD phosphors at very low dose of 5 Gy. It was found that NaMgSO₄Cl: Cu is 5.59 times and NaMgSO₄Cl: Ce is 6.18 times more sensitive as compared to standard CaSO₄: Dy. UV photo-excited luminescence from Cu to Ce doped NaMgSO₄Cl halosulphate phosphors has been investigated. The intense emission of the spectrum is assigned to electronic transitions 3d⁹4s¹→3d¹⁰ in monovalent copper ion and 5d→4f in Ce³⁺ ions. Increase in PL peak intensity suggesting that Cu and Ce play an important role in PL emission in the present matrix. These phosphors were synthesized by the wet chemical method. XRD, photoluminescence (PL) and thermoluminescence (TL) characterization of phosphors has been reported in this paper. The preparation of an inexpensive and high sensitive NaMgSO₄Cl: Cu and NaMgSO₄Cl: Ce with TL glow peaks for different concentrations are observed between 160 and 195 °C and between 200 and 225 °C, respectively, exposed to gamma-rays of ⁶⁰Co for their thermoluminescence (TL) properties. The glow curves have been recorded at a heating rate of 2 K s^?1 and irradiated at a dose rate of 0.995 kGy h^?1 for 5 Gy. In present study the trapping parameters such as order of kinetics (b), activation energy (E) and frequency factors (s) have been calculated for the 195 and 200 °C glow peaks of NaMgSO₄Cl: Cu and NaMgSO₄Cl: Ce, respectively by using Chen's method. The paper discusses the luminescence of Cu⁺ and Ce³⁺ by simple method of incorporation in NaMgSO₄Cl host.     

Luminescence investigations on sulfate apatite Na6(SO4)2FCl:RE (RE=Dy, Ce or Eu) phosphors

A new phosphor in the Cl-F system doped with Dy, Ce and Eu has been reported. Characterization of this phosphor using XRD, PL and TL techniques is described. Polycrystalline Na₆(SO₄)₂FCl:Dy; Na₆(SO₄)₂FCl:Ce and Na₆(SO₄)₂FCl:Eu phosphors prepared by a solid state diffusion method have been studied for their X-ray diffraction, photoluminescence (PL) and thermoluminescence (TL)characteristics. The PL excitation and emission spectra of phosphors were obtained. Dy³⁺ emission in the host at 475 and 570 nm is observed due to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transition, respectively, whereas the PL emission spectra of Na₆(SO₄)₂FCl:Ce phosphor shows the Ce³⁺ emission at 322 nm due to 5d→4f transition of Ce³⁺ ion. In Na₆(SO₄)₂FCl:Eu lattice, Eu²⁺ as well as Eu³⁺ emissions are observed. The emission of europium ion in this compound exhibits the blue as well as red emission. The TL glow curves of the same compounds have the simple structure with a prominent peak at 150, 175 and 200 °C. TL response, fading, reusability and trapping parameters of the phosphors are also studied. The TL glow curves of γ-irradiated Na₆(SO₄)₂FCl sample show one glow peak indicating that only one set of traps is being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The trapping parameters associated with the prominent glow peak are calculated using Chen’s half width method. The release of hole/electron from defect centers at the characteristic trap site initiates the luminescence process in these materials. The intensity of the TL glow peaks increases with increase of the added γ-ray dose to the samples.     

Synthesis and thermoluminescence characteristics of γ-irradiated K3Ca2(SO4)3F:Eu or Ce fluoride

New halophosphor K₃Ca₂(SO₄)₃F activated by Eu and Ce has been synthesized by a co-precipitation method and characterized according to its thermoluminescence. The formation of traps in rare earth doped K₃Ca₂(SO₄)₃F and the effects of γ-radiation dose on the glow curve are discussed. The glow curve of K₃Ca₂(SO₄)₃F:Ce shows a prominent single peak at 150°C, whereas K₃Ca₂(SO₄)₃F:Eu and K₃Ca₂(SO₄)₃F:Ce,Eu at 142°C and 192°C, respectively. A single glow peak indicates that there is only one set of trap being activated within the particular temperature range. The presented phosphors are also studied because of its fading, reusability and trapping parameters. There was just 2% fading during a period of 10 days, indicating no serious fading problem. Trapping parameters such as order of kinetics (b), activation energy (E) and frequency factor (S) were calculated by using Chen's half-width method. The observations presented in this paper are good for lamp phosphors as well as solid-state dosimeter.     

Investigation of thermoluminescence in Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> phosphors doped with Cu,Ag and Mg

Li2B4O7 (LBO)Cu,Ag,Mg phosphors have been prepared by the sintering technique.The roles of the Ag and Mg dopants in the phosphors have been studied using the methods of thermoluminescence (TL) glow curves and TL 3D spectra. The results indicated that proper concentrations of Ag and Mg can enhance the TL of LBOCu.It was also indicated that the intensity of TL peak at ～130℃ is reduced with the increasing Ag concentration, and enhanced with the increasing Mg concentration.From the TL 3D spectra, three emission bands (λ1 = 421 nm,λ2 = 380 nm, λ3 = 350nm) were observed the intensity of low energy emission band is reduced and that of the high energy is enhanced with the increasing dopant Ag; on the contrary, the intensity of low energy emission band is enhanced and that of the high energy one is reduced with the increasing dopant Mg.     

Dosimetric properties of rare earth doped LiCaBO3 thermoluminescence phosphors

Lithium Calcium borate (LiCaBO₃) polycrystalline thermoluminescence (TL) phosphor doped with rare earth (RE³⁺) elements has been synthesized by high temperature solid state diffusion reaction. The reaction has produced a very stable crystalline LiCaBO₃:RE³⁺ phosphors. Among these RE³⁺ doped phosphors thulium doped material showed maximum TL sensitivity with favorable glow curve shape. TL glow curve of gamma irradiated LiCaBO₃:Tm³⁺ samples had shown two major well-separated glow peaks at 230 and 430 °C. The glow peak at 430 °C is almost thrice the intensity of the glow peak at 230 °C. The TL sensitivity of the phosphor to gamma radiation was about eight times that of TLD-100 (LiF). Photoluminescence and TL emission spectra showed the characteristic Tm³⁺ peaks. TL response to gamma radiation dose was linear up to 10³ Gy. Post-irradiation TL fading on storage in room temperature and elevated temperatures was studied in LiCaBO₃:Tm³⁺ phosphor.     

Electroluminescence of CaSO4: Sm phosphors

CaSO₄ phosphors activated with Sm³⁺ impurity in varying concentrations have been prepared and their electroluminescence systematically studied. The voltage and frequency dependence of brightness is discussed and conclusions are drawn regarding the possible mechanism involved in the process.     

Kinetics of luminescence as revealed from photo-, thermo- and electro-luminescence studies on CaS : Ag phosphors

Phosphorescence decay, thermoluminescence and electroluminescence of CaS : Ag phosphors prepared with a varying amount of silver as activator have been studied at room temperature, 301 K. The observations have been analysed to obtain the information about the type of kinetics involved in the luminescence process. In addition to this, the effect of the addition of an activator on the luminescence behaviour of the phosphors and on the distribution of trapping levels is discussed.     

Radiation damage in polyacrylonitrile

Radiation damage in polyacrylonitrile (PAN) has been studied in the temperature range 273 to 420 K using thermoluminescence, electron spin resonance and optical absorption techniques. ATL glow peak has been observed with maximum at 362 K. The species responsible for theTL glow peak has been identified to be due to the free radical -CH₂-CH(CN)-ĊH-CH(CN)-CH₂-by correlation with the data obtained by the temperature variation ofESR and optical absorption spectra of thex-irradiated, pre- and post-x-irradiated and thermally-treated samples. A mechanism of formation of network structures accelerated by the free radicals formed on irradiation has been investigated to explain the optical absorption spectra. TheTL glow peak is analysed by various methods and corresponds to an activation energy of 1 eV, following second order kinetics.     

掺稀土元素Dy和Mn,P,Cu的MgSO4的热释发光光谱

实验测定了MgSO₄:Dy,Mn和MgSO₄:Dy,P以及MgSO₄:Dy,P ,Cu等的热释光磷光体的三维发光谱.结果表明,掺入Dy的MgSO₄磷光体的热释发 光谱线的波长与Dy³⁺离子的能级跃迁相关,Dy³⁺为热释光主要发光 中心.MgSO₄中只掺入Mn时,温度在140℃和190℃附近呈现波长为660nm宽范围的 连续发光带,这是Mn形成的发光中心的 关键词： 热释发光光谱 稀土元素镝 硫酸镁     

Relative thermoluminescence effects of alpha‐ and beta‐ radiation

Abstract

A study has been made of the relative thermoluminescence response to α- and β-radiation of six phosphors (two types of natural fluorite, CaF₂: Mn, CaF₂: Tb, CaSO₄: Mn and quartz) using samples which are thin compared to the range of the α-particles. The α- and β-radiations induce the same glow peaks, but at low doses (<100 rads) the TL response per rad of α-radiation (3.7 MeV) is less than that per rad of β-radiation in all the glow peaks studied. The α-efficiency ranges from 53 per cent for CaF₂: Mn to 2 per cent for quartz (110°C peak) at 3.7 MeV and decreases with decreasing α-particle energy. At higher doses (10⁶?10⁷ rads) the TL responses to α- and β-radiation become equal within 15 per cent; most of the glow peaks are in or near saturation at these doses. The higher the β-dose at which a peak saturates, the higher is the α-efficiency (at low doses) of that peak. The results support the interpretation that the α-efficiency is low because the phosphor is near or in saturation in the localized region near the α-path. This interpretation is given quantitative support by a theoretical calculation of the localized energy-density.